Methylenedioxy substituted benzene derivatives

ABSTRACT

Compounds of the formula ##STR1## wherein N REPRESENTS THE NUMBERS 0 OR 1, 
     Z represents oxygen, ##STR2## or sulphur R 1  represents the groups ##STR3## wherein R 5  represents hydrogen, halogen, C 1  -C 5  -alkyl, ethynyl, C 1  -C 4  -alkylthio, C 1  -C 5  -alkoxy, C 3  -C 5  -alkenyloxy, C 3  -C 5  -haloalkenyloxy, C 3  -C 5  -alkynyloxy, nitro, cyano, C 2  -C 5  -alkoxycarbonyl, C 3  -C 5  -alkenyloxycarbonyl, C 3  -C 5  -alkynyloxycarbonyl, C 1  -C 3  -alkanoyl, C 1  -C 4  -alkylcarbamoyl, (di-C 1  -C 4  -alkyl)carbamoyl, 
     R 6  represents hydrogen, halogen, methyl, ethyl, isopropyl or methoxy, and 
     R 8  represents hydrogen or n-propyl, 
     R 2  represents hydrogen, methyl or ethyl, 
     R 3  and R 4  each represent hydrogen, methyl, ethyl, methoxy, ethoxy, nitro or halogen, and 
     R 7  represents hydrogen or C 1  -C 2  -alkanoyl. 
     And their use for combating insects and members of the order acarina are disclosed.

This is a division of application Ser. No. 460,404 filed on Apr. 12,1974, now U.S. Pat. No. 3,187,102.

The present invention relates to diphenyl ethers, to processes for theirpreparation, and to their use in pest control.

The said diphenyl ethers have the formula ##STR4## wherein N REPRESENTSTHE NUMBERS 0 OR 1,

Z represents oxygen, ##STR5## or sulphur R₁ represents the groups##STR6## wherein R₅ represents hydrogen, halogen, C₁ -C₅ -alkyl,ethynyl, C₁ -C₄ -alkylthio, C₁ -C₅ -alkoxy, C₃ -C₅ -alkenyloxy, C₃ -C₅-haloalkenyloxy, C₃ -C₅ -alkynyloxy, nitro, cyano, C₂ -C₅-alkoxycarbonyl, C₃ -C₅ -alkenyloxycarbonyl, C₃ -C₅ -alkynyloxycarbonyl,C₁ -C₃ -alkanoyl, C₁ -C₄ -alkylcarbamoyl, (di-C₁ -C₄ -alkyl)carbamoyl,

R₆ represents hydrogen, halogen, methyl, ethyl, isopropyl or methoxy,and

R₈ represents hydrogen or n-propyl,

R₂ represents hydrogen, methyl or ethyl,

R₃ and R₄ each represent hydrogen, methyl, ethyl, methoxy, ethoxy, nitroor halogen, and

R₇ represents hydrogen or C₁ -C₂ -alkanoyl.

By halogen is meant fluorine, chlorine, bromine or iodine. The alkyl,alkylthio, alkoxy, alkenyloxy, haloalkenyloxy or alkynyloxy groups givenunder R₅ are straight-chain or branched-chain. Examples of such groupsare: methyl, ethyl, n-propyl, isopropyl, methylthio, methoxy, ethoxy,allyloxy, β-chloroallyloxy, γ-chloroallyloxy, propargyloxy or1-butin-3-yloxy. The alkyl, alkoxy, alkenyloxy or alkynyloxy parts of analkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, ordialkylcarbamoyl group R₅ can be branched-chain or straight-chain.Examples of alkoxy, alkenyloxy, alkynyloxycarbonyl or dialkylcarbamoylgroups are: carbomethoxy, carbethoxy, allyloxycarbonyl,propargyloxycarbonyl or diethylcarbamoyl. Examples of alkanoyl groupsdenoted by R₅ and R₇ are: formyl, acetyl or propionyl.

Preferred compounds of formula I by virtue of their action are thosewherein

n represents the number O,

Z represents oxygen or sulphur,

R₁ represents the groups ##STR7## wherein R₅ represents hydrogen,methyl, ethyl, propyl, isopropyl, fluorine, chlorine, bromine, iodine,nitro, methoxy, ethoxy, methylmercapto, propargyloxy, allyloxy, C₂ -C₃-alkoxycarbonyl, propargyloxycarbonyl, acetyl or diethylcarbamoyl,

R₆ represents hydrogen, chlorine, methyl, ethyl or methoxy and

R₈ represents hydrogen or n-propyl, and

R₂ represents hydrogen or methyl and

R₃ and R₄ each represent hydrogen, chlorine, methyl, methoxy or ethoxy.

The compounds of formula I can be prepared according to the followingmethods known per se by alkylation of a 4-phenoxyphenol or4-phenoxyphenolate, of a 4-phenoxythiophenol or 4-phenoxy-thiophenolateor of a 4-phenoxyaniline II or IV with a halide III, in the presence ofa base or of an acid-binding agent: ##STR8## (2) If R₇ representshydrogen: ##STR9## (3) Process for the preparation of compounds offormula I wherein Z = --NR₇ --, n = O, R₂ = H, R₇ = hydrogen, formyl oracetyl, and R₁, R₃ and R₄ have the meanings given for formula I:

A primary aromatic amine V is condensed, in a known manner, with anaromatic, optionally substituted aldehyde VI, optionally in the presenceof an acid catalyst, such as, e.g. p-toluenesulphonic acid or sulphuricacid, to an azomethine derivative VII, with the separation of water. The--N═C bond of the azomethine VII is hydrogenated, e.g. catalytically inthe presence of a metal catalyst, such as, e.g. finely divided nickel,palladium or platinum. The phenoxy-aniline derivative VIII can, ifrequired, be further treated with an acylating agent, such as, e.g.carboxylic acid anhydrides or carboxylic acid chlorides, wherebycompounds of formula IX are obtained. ##STR10##

In the above process, condensation of a compound of formula X with acompound of formula XI with catalytic splitting-off of water isperformed preferably at a temperature of 60° - 110° C.Dicyclohexylcarbodiimide, for example, can be used as the agentsplitting off water.

In formulae II to XI, the symbols R₁ to R₄ and n have the meanings givenfor formula I, R'₇ stands for formyl or acetyl, Z' for oxygen orsulphur, X for halogen, especially chlorine or bromine, and Me for ametal of the 1st or 2nd main group of the periodic system, particularlysodium, potassium or calcium.

Suitable acid-binding agents or bases are, e.g. tertiary amines such astrialkylamines, pyridine or dialkyllanilines; also inorganic bases suchas hydrides or hydroxides; and alkoxides and carbonates of alkali metalsand alkaline-earth metals. Processes 1 and 2 are performed as a reactiontemperature of between -10° and 130° C, preferably between 10° and 80°C, undernormal pressure and in the presence of solvents or diluents.

Suitable solvents or diluents are, e.g. ethers such as diethyl ether,diisopropyl ether, 1,2-dimethoxyethane, dioxane or tetrahydrofuran;N,N-dialkylated carboxylic acid amides such as dimethylformamide;aliphatic and aromatic hydrocarbons, particularly benzene, toluene,xylenes or ethylbenzene; ketones such as acetone, methylethyl ketone orcyclohexanone, as well as hexamethylphosphoric acid triamide ordimethylsulphoxide.

The starting materials of formulae II to VI, X and XI are knowncompounds, or can be prepared by methods analogous to those described inthe literature. The azomethines of formula VII are in some cases newcompounds.

The compounds of formula I are suitable for the control of insects ofthe families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae,Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae,Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae,Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae,Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae,Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae andPulicidae, as well as acarids of the families: Ixodidae, Argasidae,Tetranychidae and Dermanyssidae.

The insecticidal action of the said compounds can be appreciably widenedand adapted to suit given circumstances by the addition of otherinsecticides and/or acaricides. Suitable additives are, e.g.:

organic phosphorus compounds,

nitrophenols and derivatives,

formamidines, ureas,

carbamates or

chlorinated hydrocarbons.

The compounds of formula I can be used on their own or together withsuitable carriers and/or additives. Suitable carriers and additives maybe solid or liquid, and they correspond to the substances common informulation practice, such as, e.g. natural or regenerated substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisers.

For application, the compounds of formula I can be processed into theform of dusts, emulsion concentrates, granulates, dispersions, sprays orsolutions, the formulation of these preparations being effected in amanner commonly known in practice.

The agents according to the invention are prepared in a manner known perse by the intimate mixing and/or grinding of active substances offormula I with suitable carriers, optionally with the addition ofdispersing agents or solvents which are inert to the active substances.The active substances can be obtained and used in the following forms:

solid preparations:

dusts, scattering agents, granulates, coated granulates, impregnatedgranulates and homogeneous granulates;

liquid preparations:

(a) water-dispersible active-substance concentrates: wettable powders,pastes or emulsions;

(b) solutions.

The content of active substance in the described agents is between 0.1and 95 %.

The active substances of formula I can be formulated, for example, asfollows:

Dusts:

The following substances are used in the preparation of a) a 5% dust,and b) a 2% dust:

    ______________________________________                                        a)    5      parts of active substance,                                             95     parts of talcum;                                                 b)    2      parts of active substance,                                             1      part of highly dispersed silicic acid,                                 97     parts of talcum.                                                 ______________________________________                                    

The active substances are mixed and ground with the carriers.

Granulate:

The following substances are used to prepare a 5% granulate:

    ______________________________________                                        5        parts of active substance,                                           0.25     part of epichlorohydrin,                                             0.25     part of cetyl polyglycol ether,                                      3.50     parts of polyethylene glycol,                                        91       parts of kaolin (particle size 0.3-0.8 mm).                          ______________________________________                                    

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The solution thus obtained is sprayed onto kaolin, and theacetone subsequently evaporated off in vacuo.

Wettable powder:

The following constituents are used for the preparation of a) a 40%, b)and c) a 25%, and d) a 10% wettable powder:

    ______________________________________                                        a)    40     parts of active substance,                                             5      parts of sodium lignin sulphonate,                                     1      part of sodium dibutyl-naphthalene sulphonate,                         54     parts of silicic acid;                                           b)    25     parts of active substance,                                             4.5    parts of calcium lignin sulphonate,                                    1.9    parts of Champagne chalk/hydroxyethyl cellulose                               mixture (1:1),                                                         1.5    parts of sodium dibutyl naphthalene sulphonate,                        19.5   parts of silicic acid,                                                 19.5   parts of Champagne chalk,                                              28.1   parts of kaolin;                                                 c)    25     parts of active substance,                                             2.5    parts of isooctylphenoxy-polyoxyethylene-ethanol,                      1.7    parts of Champagne chalk/hydroxyethyl                                         cellulose mixture (1:1),                                               8.3    parts of sodium aluminium silicate,                                    16.5   parts of kieselguhr,                                                   46     parts of kaolin;                                                 d)    10     parts of active substance,                                             3      parts of a mixture of the sodium salts of                                     saturated fatty alcohol sulphates,                                     5      parts of naphthalenesulphonic acid/formaldehyde                               condensate,                                                            82     parts of kaolin.                                                 ______________________________________                                    

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. Wettable powders are obtained which can be diluted with waterto give suspensions of any desired concentration.

Emulsifiable concentrates:

The following substances are used to prepare a) a 10% and b) a 25%emulsifiable concentrate:

    ______________________________________                                        a)    10     parts of active substance,                                             3.4    parts of epoxidised vegetable oil,                                     3.4    parts of a combination emulsifier consisting                                  of fatty alcohol polyglycol ether and alkylaryl-                              sulphonate calcium salt,                                               40     parts of dimethylformamide,                                            43.2   parts of xylene;                                                 b)    25     parts of active substance,                                             2.5    parts of epoxidised vegetable oil,                                     10     parts of an alkylarylsulphonate/fatty alcohol                                 polyglycol ether mixture,                                              5      parts of dimethylformamide,                                            57.5   parts of xylene.                                                 ______________________________________                                    

From these concentrates it is possible to prepare, by dilution withwater, emulsions of any desired concentration.

Spray:

The following constituents are used to prepare a 5% spray:

    ______________________________________                                        5       parts of active substance,                                            1       part of epichlorhydrin,                                               94      parts of ligroin (boiling limits 160-190° C).                  ______________________________________                                    

EXAMPLE 1 (A) Preparation of1-phenoxy-4-(3',4'-methylenedioxy)-benzyloxybenzene

18 g of finely powdered anhydrous potassium carbonate is added to asolution of 18.6 g of 4-hydroxy-diphenyl ether in 100 ml of anhydrousacetone, and the mixture heated to the reflux temperature of theacetone. After half an hour, the solution of 17.1 g of3,4-methylenedioxychloromethylbenzene in 100 ml of toluene is addeddropwise within one hour, and the reaction mixture refluxed for afurther 18 hours. The reaction solution is then filtered off from thesolid phase, and the solvent completely removed in vacuo from thefiltrate. The residue is dissolved in acetic acid ethyl ester/toluene,ca. 1:1; the solution is repeatedly washed with ice-cold 10% potassiumhydroxide solution and afterwards with water and saturated sodiumchloride solution until neutral. After drying of the organic phase bymeans of sodium sulphate, the solvent is completely removed in vacuo,and the residue, solidifying in crystalline form, recrystallised twicein acetonitrile to obtain1-phenoxy-4-(3',4'-methylenedioxy)-benzyloxybenzene, M.P. 90° - 91° C.

(B) Preparation of 4-phenoxy-N-(3,4-methylenedioxybenzyl)-aniline

The solution of 47.6 g of4-phenoxy-(3,4-methylene-dioxybenzylidene)-aniline in 500 ml of puremethanol and 450 ml of methylcellosolve is, after the addition of 3 g ofplatinum oxide, catalytically hydrogenated at 20°- 30° C to effect theabsorption of 3.36 l of hydrogen. The catalyst is filtered off, and thesolvent removed in vacuo from the filtrate. The residue ischromatographically purified through silica gel (eluant: ether/hexane1:1), and the resulting pure4-phenyl-N-(3,4-methylenedioxybenzyl)-aniline recrystallised inether/hexane, M.P. 95° - 96° C.

The starting material used for catalytic hydrogenation,4-phenoxy-(3,4-methylenedioxy-benzylidene)-aniline, is prepared asfollows: the solution of 75 g of 3,4-methylenedioxy-benzaldehyde(piperonal) and 92.5 g of 4-aminodiphenyl ether in 500 ml of benzene isrefluxed, with separation of water, for 8 hours. After the water hasbeen completely separated, the reaction mixture is concentrated byevaporation; the crystals precipitated after cooling to about + 5° C arefiltered off under suction; the crystal mass is recrystallised firstlyin anhydrous benzene and subsequently in acetonitrile to thus obtainpure 4-phenoxy-(3,4-methylenedioxybenzylidene)-aniline, M.P. 89° - 91°C. The following azomethine derivatives are prepared in a manneranalogous to that described above:

    __________________________________________________________________________                                         Physical                                 Compounds                            data                                     __________________________________________________________________________     ##STR11##                           M.P.: 76 - 77° C                   ##STR12##                           M.P.: 79 - 80° C                   ##STR13##                           M.P.: 104 - 106° C                 ##STR14##                           M.P.: 120 - 121° C                __________________________________________________________________________

(C) Preparation of4-phenoxy-N-acetyl-N-(3,4-methylenedioxybenzyl)-aniline

3.2 ml of acetyl chloride dissolved in 10 ml of anhydrous benzene isadded dropwise at 0° - 5° C in the course of one hour, with stirring, toa solution of 12.7 g of 4-phenoxy-N-(3,4-methylenedioxybenzyl)-anilineand 6 g of N-ethyl-diisopropylamine in 100 ml of anhydrous benzene. Thewhole is subsequently heated to room temperature and stirred for afurther 8 hours. The precipitated N-ethyl-diisopropylamine-hydrochlorideis separated by filtration; the filtrate is washed with 10% sodiumcarbonate solution and then with water. After drying of the organicphase by means of sodium sulphate, the benzene is distilled off invacuo, and the residue recrystallised in hexane to obtain4-phenoxy-N-acetyl-N-(3,4-methylenedioxybenzyl)-aniline, M.P. 75°- 76°C.

                                      Table 1                                     __________________________________________________________________________    The following further compounds are prepared in a manner                      analagous to that previously described:                                                                               Physical                              Compounds                               data                                  __________________________________________________________________________     ##STR15##                              M.P. 55 - 57° C                 ##STR16##                              n.sub.D.sup.20 = 1,5840                ##STR17##                              M.P.: 69 - 70° C                ##STR18##                              M.P.: 126 - 128° C              ##STR19##                              M.P.: 71 - 72° C                ##STR20##                              M.P.: 60 - 61° C                ##STR21##                              n.sub.D.sup.20 = 1,6003                ##STR22##                              M.P.: 107 - 109° C              ##STR23##                              n.sub.D.sup.20 = 1,5801                ##STR24##                              M.P.: 60 - 62° C                ##STR25##                              M.P.: 45 -  47° C               ##STR26##                              M.P.: 108 - 109° C              ##STR27##                              M.P.: 65 - 67° C                ##STR28##                              M.P.: 60 - 61° C                ##STR29##                              M.P.: 103 - 104° C              ##STR30##                              M.P.: 97 - 98° C                ##STR31##                              M.P.: 50 - 51°  C               ##STR32##                              n.sub.D.sup.20 = 1,6313                ##STR33##                              M.P.: 112 - 113° C              ##STR34##                              M.P.: 94 - 95° C                ##STR35##                              M.P.: 43 - 45° C                ##STR36##                              M.P.: 68 - 69° C                ##STR37##                              M.P.: 55 - 56° C                ##STR38##                              M.P.: 61 - 62° C                ##STR39##                              M.P.: 89 - 90° C                ##STR40##                              M.P.: 74 - 75° C                ##STR41##                              M.P.: 81 - 83° C                ##STR42##                              M.P.: 90 - 91° C                ##STR43##                              M.P.: 44 - 45° C                ##STR44##                              M.P.: 90 - 91° C                ##STR45##                              M.P.: 66 - 67° C                ##STR46##                              M.P.: 103 - 105° C              ##STR47##                              M.P.: 45 - 46° C                ##STR48##                              n.sub.D.sup.20 : 1,5858                ##STR49##                              n.sub.D.sup.20 = 1,5988                ##STR50##                              M.P.: 112 - 113° C              ##STR51##                              M.P.: 133 - 134° C              ##STR52##                              M.P.: 41 - 43° C                ##STR53##                              M.P.: 59 - 60° C                ##STR54##                              n.sub.D.sup.20 = 1,6064                ##STR55##                              M.P. 60 - 61° C                 ##STR56##                              M.P.: 92 - 93° C                ##STR57##                              M.P.: 79 - 80° C                ##STR58##                              M.P. 90 - 91° C                 ##STR59##                              n.sub.D.sup.20 = 1,5972                ##STR60##                              n.sub.D.sup.20 = 1,5778                ##STR61##                                                                     ##STR62##                                                                     ##STR63##                              M.P.: 76 - 77° C                ##STR64##                                                                     ##STR65##                                                                     ##STR66##                                                                     ##STR67##                                                                     ##STR68##                                                                     ##STR69##                              M.P.: 142 - 144° C              ##STR70##                              n.sub.D.sup.20 : 1,5893                ##STR71##                                                                     ##STR72##                                                                    __________________________________________________________________________

EXAMPLE 2 (A) Contact action on Dysdercus-fasciatus larvae

A specific amount of a 0.1% acetonic active-substance solution(corresponding to 10 mg of active substance per square meter) wastransferred by pipet to an aluminium dish and uniformly distributed.After evaporation of the acetone, 10 larvae in the 5th stage ofDysdercus fasciatus were placed into the treated dish containing feedand moist cotton wool. The dish was then covered with a perforated lid.After about 10 days, i.e. as soon as the control insects had moultedinto adults, the test insects were examined to determine the number ofnormal adults.

Compounds according to Example 1 and Table 1 exhibited a good action inthe above test.

(B) Contact action on Aedes-aegypti larvae

About 20 two-day-old larvae of the yellow-fever mosquito (Aedes aegypti)were placed in position in a beaker containing a solution of the activesubstance (concentration 5 ppm). The beaker was then covered with aperforated lid. After the control insects had moulted into adults, thetest insects were examined and the percentage of normal adults incomparison with the control adults determined.

Compounds according to Example 1 and Table 1 exhibited a good action inthe above test.

(C) Contact action on Tenebrio-molitor pupae

A specific amount of a 0.1% acetonic active-substance solutioncorresponding to 10 mg of active substance per square meter wastransferred by pipet into an aluminium dish and uniformly distributed.After evaporation of the acetone, 10 freshly formed pupae were placed onthe treated surface, and the dish covered with a perforated lid. Afterthe control insects had left the cocoon as imagines, the test insectswere examined to determine the number of normal adults.

Compounds according to Example 1 and Table 1 exhibited a good action inthe above test.

EXAMPLE 3 (A) Action against Musca domestica

An amount in each case of 50 g of CSMA maggot substrate was weighed offin beakers. For each active substance, 2.5 ml of a 1% acetonic solutionin the respective substance was transferred twice to 50 g of maggotsubstrate each time. After a thorough mixing of the treated substrate,the solvent was allowed to evaporate off. There were then deposited peractive substance in each case 25 one-, two- and three-day-old maggotsand about 50 fly eggs. After completion of pupation, the pupae wereflushed out and counted. After a period of ten days, the number ofemerged flies was determined and hence any effect on metamorphosisestablished.

Compounds according to Example 1 and Table 1 exhibited in this test agood action against Musca domestica.

(B) Action against Ephestia kuhniella

50 g of wheat flour was made up in two beakers with a specific amount ofactive substance to give a 5% dust, the concentration thus being 0.05%.Into each beaker (25 g of flour) were placed 10 larvae of Ephestiakuhniella. The course of population was ascertained over a period of 8weeks and the number of moths determined.

Compounds according to Example 1 and Table 1 exhibited a good action inthe test against Ephestia kuhniella.

EXAMPLE 4 Action against red spider mites

Phaseolus vulgaris (bush beans) were infested, 12 hours before the testfor acaricidal action, with an infested piece of leaf from a massculture of Tetranychus urticae. The tranferred mobile stages weresprayed with the emulsified test preparations, at a concentration of0.04%, by means of a chromatography-sprayer in a manner ensuring norunning off of the spray liquor. An assessment was made after 2 to 7days, by examination under a binocular, of the living and of the deadlarvae, adults and eggs, and the results expressed in percentages. Thetreated plants were kept during the holding time in greenhousecompartments at 25° C.

The compounds according to Example 1 and Table 1 exhibited in the abovetest a good action against eggs, larvae and adults of Tetranychusurticae.

What we claim is:
 1. A compound of the formula ##STR73## wherein nrepresents the numbers 0 or 1,Z represents oxygen, ##STR74## or sulphur,R₁ represents ##STR75## R₈ represents hydrogen or n-propyl, R₂represents hydrogen, methyl or ethyl, R₃ and R₄ each represent hydrogen,methyl, ethyl, methoxy, ethoxy, nitro or halogen, and R₇ representshydrogen or C₁ -C₂ -alkanoyl.
 2. The compound according to claim 1whereinn represents the number 0, Z represents oxygen or sulphur, R₁represents ##STR76## wherein R₈ represents hydrogen or n-propyl, R₂represents hydrogen or methyl, and R₃ and R₄ each represent hydrogen,chlorine, methyl, methoxy or ethoxy. 3.1-Phenoxy-4-[(3',4'-methylenedioxy)-benzyloxy]benzene according to claim2.
 4. 1-Phenoxy-4-[(2'-n-propyl-3',4'-methylenedioxy)-benzyloxy]benzeneaccording to claim
 2. 5.4-Phenoxy-1[(3',4'-methylenedioxy)-benzyl]-aniline according to claim 1.6. 1-Phenoxy-4-[(3',4'-methylenedioxy)-benzylthio-] benzene according toclaim
 2. 7. 5-Phenoxy-2-[(3',4'-methylenedioxy)-benzyloxy]-tolueneaccording to claim
 2. 8.1-Phenoxy-4-[(α-methyl-3',4'-methylenedioxy)-benzyloxy]benzene accordingto claim
 2. 9.1-(2'-Toluyloxy)-4-[(3',4'-methylenedioxy)-benzyloxy]-benzene accordingto claim
 2. 10.1-(3'-Toluyloxy)-4-[(3',4'-methylenedioxy)-benzyloxy]-benzene accordingto claim
 2. 11. An insecticidal or acaricidal agent containing aninsecticidal or acaricidal effective amount of a compound of claim 1together with a suitable carrier therefor.
 12. A method for the controlof insects or members of the order Acarina which comprises applying tothe locus thereof an insecticidal or acaricidal effective amount of acompound of claim 1.